CN115536982A - Epoxy composite material with nonlinear conductivity and dielectric property and preparation method and application thereof - Google Patents
Epoxy composite material with nonlinear conductivity and dielectric property and preparation method and application thereof Download PDFInfo
- Publication number
- CN115536982A CN115536982A CN202211144268.3A CN202211144268A CN115536982A CN 115536982 A CN115536982 A CN 115536982A CN 202211144268 A CN202211144268 A CN 202211144268A CN 115536982 A CN115536982 A CN 115536982A
- Authority
- CN
- China
- Prior art keywords
- tio
- pda
- composite material
- nano
- epoxy composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses an epoxy composite material with nonlinear conductivity and dielectric property, and a preparation method and application thereof. The epoxy composite material comprises an epoxy resin matrix and filled BT @ TiO 2 @ PDA nanoparticles and filled boron nitride nanosheets, BT @ TiO 2 The @ PDA nano-particle sequentially comprises a nano barium titanate core, a nano titanium dioxide coating layer and a polydopamine coating layer from inside to outside, and boron nitride nano-sheets are transversely and directionally arranged in an epoxy resin matrix. The preparation method of the epoxy composite material comprises the following steps: mixing BT @ TiO 2 @ PDA nanoparticle, boron nitride nanosheet, epoxy resin, curing agent andand injecting the mixture of the accelerant into a mould for precuring and hot-pressing curing to obtain the epoxy composite material. The epoxy composite material has the advantages of non-linear conductivity and non-linear dielectric property, and high breakdown strength, and is suitable for high-voltage electrical equipment.
Description
Technical Field
The invention relates to the technical field of epoxy resin composite materials, in particular to an epoxy composite material with nonlinear conductivity and dielectric property, and a preparation method and application thereof.
Background
With the continuous improvement of voltage level, local discharge and local electric field distortion become key factors for limiting the miniaturization of high-voltage electrical equipment, and the composite material with nonlinear conductivity and nonlinear dielectric property is considered as an effective method for uniform electric field due to the outstanding electric field adaptive regulation capability, thereby drawing extensive attention of researchers.
The field nonlinear composite material can be divided into two types of a capacitance field gradient composite material and a resistance field gradient composite material according to application occasions, the capacitance field gradient composite material with nonlinear dielectric constant can flexibly adjust electric field distribution in alternating current application, and the resistance field gradient composite material with nonlinear conductivity in direct current application can rapidly dissipate accumulated space charges so as to avoid local electric field distortion. At present, in order to obtain excellent nonlinear dielectric properties, ferroelectric particles having a high dielectric constant (e.g., baTiO) are generally used 3 、SrTiO 3 、PbTiO 3 Etc.) to prepare a polymer composite. However, due to the serious mismatch between the dielectric constants of the ferroelectric particles and the polymer matrix, the resulting composite material tends to have high dielectric loss and leakage current, which makes it difficult to apply the composite material to high-voltage equipment. In addition, the capacitive field gradient composite material composed of ferroelectric particles and polymers generally does not have nonlinear conductive characteristics, and the problem of charge accumulation is difficult to solve. The resistive field gradient composite material has excellent nonlinear conductivity by adding a large amount of semiconductor filler into a polymer, but also can cause the breakdown strength of the material to be reduced, and the obtained resistive field gradient composite material does not show nonlinear dielectric constant characteristics.
Therefore, it is very important to develop a composite material with both non-linear conductivity and dielectric property and high breakdown strength.
Disclosure of Invention
The invention aims to provide an epoxy composite material with nonlinear electrical conductivity and dielectric property, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
an epoxy composite material with non-linear electric and dielectric properties is composed of epoxy resin matrix, filled BT @ TiO 2 @ PDA nanoparticles and filled boron nitride nanosheets; the BT @ TiO 2 The composition of the @ PDA nano-particle sequentially comprises a nano barium titanate core, a nano titanium dioxide coating layer and a polydopamine coating layer from inside to outside; the boron nitride nanosheets are transversely and directionally arranged in the epoxy resin matrix.
Preferably, BT @ TiO in the epoxy composite material with nonlinear conductivity and dielectric property 2 The mass percentage content of the @ PDA nano-particles is 5% -30%.
Further preferably, BT @ TiO in the epoxy composite material with nonlinear conductivity and dielectric property 2 The mass percentage content of the @ PDA nano-particles is 20-30%.
Preferably, the mass percentage of the boron nitride nanosheets in the epoxy composite material with nonlinear conductivity and dielectric property is 4-6%.
Preferably, the BT @ TiO 2 The particle size of the @ PDA nano-particles is 80 nm-100 nm.
Preferably, the plate diameter of the boron nitride nanosheet is 100nm to 600nm.
Preferably, the BT @ TiO 2 @ PDA nanoparticles were made by the following method:
1) Dispersing nano barium titanate particles in an organic solvent, adding ammonia water, adding tetrabutyl titanate solution for reaction, separating out a solid product, and annealing to obtain BT @ TiO 2 A nanoparticle;
2) Mixing BT @ TiO 2 Dispersing the nano particles in Tris buffer solution, adding dopamine hydrochloride, and reacting to obtain BT @ TiO 2 @ PDA nanoparticles.
Further preferably, the BT @TiO 2 @ PDA nanoparticles are passed throughThe preparation method comprises the following steps:
1) Ultrasonically dispersing nano barium titanate particles in an organic solvent, adding ammonia water, dropwise adding tetrabutyl titanate solution for reaction, centrifugally separating out a solid product, washing with alcohol, drying and annealing the solid product to obtain BT @ TiO 2 A nanoparticle;
2) Mixing BT @ TiO 2 Dispersing the nano particles in Tris buffer solution, adding dopamine hydrochloride, reacting, filtering to separate out solid products, washing and freeze-drying the solid products to obtain BT @ TiO 2 @ PDA nanoparticles.
Preferably, the particle size of the nano barium titanate particles in the step 1) is 70nm to 90nm.
Preferably, the organic solvent in step 1) is at least one of ethanol and isopropanol.
Preferably, the reaction in the step 1) is carried out at 40-60 ℃, and the reaction time is 20-30 h.
Preferably, the annealing treatment in the step 1) is carried out at 500-600 ℃, the annealing atmosphere is air atmosphere, and the annealing time is 2-4 h.
Preferably, the reaction in the step 2) is carried out at 50-70 ℃, and the reaction time is 20-30 h.
Preferably, the freeze drying in the step 2) is carried out at the temperature of-60 ℃ to-40 ℃ and under the pressure of 0.0001Pa to 0.0002Pa, and the freeze drying time is 24h to 48h.
A method for preparing the epoxy composite material with nonlinear conductivity and dielectric property comprises the following steps: mixing BT @ TiO 2 And dispersing the @ PDA nano particles and the boron nitride nano sheets in an organic solvent, adding epoxy resin, heating and stirring until the organic solvent is completely volatilized, adding a curing agent and an accelerator, injecting the obtained mixture into a mold, and then performing pre-curing and hot-pressing curing to obtain the epoxy composite material with nonlinear conductivity and dielectric property.
Preferably, the organic solvent is at least one of N, N-Dimethylformamide (DMF) and acetone.
Preferably, the mass ratio of the epoxy resin, the curing agent and the accelerator is 100.
Preferably, the epoxy resin is at least one of a cycloaliphatic epoxy resin and a bisphenol a type epoxy resin.
Preferably, the curing agent is at least one of methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride.
Preferably, the accelerant is at least one of 2,4,6-tris (dimethylaminomethyl) phenol, triethylamine and 2-ethyl-4-methylimidazole.
Preferably, the pre-curing is carried out at the temperature of 95-105 ℃, and the pre-curing time is 40-80 min.
Preferably, the hot-press curing is performed by the following specific operations: curing for 40-80 min under the conditions that the temperature is 110-120 ℃ and the pressure is 10-20 MPa, and then continuing curing for 100-150 min after heating to 130-140 ℃.
Use of an epoxy composite material having nonlinear electrical conductivity and dielectric properties as described above in high voltage electrical equipment.
The beneficial effects of the invention are: the epoxy composite material has the advantages of non-linear conductivity and non-linear dielectric property, and high breakdown strength, and is suitable for high-voltage electrical equipment.
Specifically, the method comprises the following steps:
1) BT @ TiO is added into the epoxy composite material 2 The nano-PDA particles are used as nano-filler, the nano-Barium Titanate (BT) core has high dielectric constant and low dielectric loss, the field dielectric nonlinearity of the composite material can be realized, the inorganic semiconductor nano-titanium dioxide coating layer has low dielectric constant and high conductivity, the dielectric constant of the composite material can be reduced on one hand, the field conductance nonlinearity of the composite material can be realized on the other hand, the organic semiconductor Polydopamine (PDA) coating layer can form gradient dielectric constant and enhance the compatibility of a microscopic interface, the local electric field distortion of the nano-filler and a matrix interface can be effectively weakened, and the PDA as an organic semiconductor can maintain the nonlinear conductance characteristic;
2) The Boron Nitride Nanosheets (BNNSs) arranged in a transverse orientation mode are added into the epoxy composite material and serve as a breakdown phase growth inhibitor, so that the electric stress can be prevented from developing downwards (namely longitudinally), the breakdown path can be effectively prolonged, and the breakdown strength of the composite material can be improved.
Drawings
FIG. 1 shows BT, BT @ TiO in example 1 2 And BT @ TiO 2 FTIR plot of @ PDA.
FIG. 2 is BT @ TiO in example 1 2 TEM and mapping of @ PDA.
FIG. 3 is BT @ TiO of example 1 2 XPS plots for @ PDA.
FIG. 4 is EP/BT @ TiO of example 1 2 @ PDA-OB and EP/BT @ TiO of comparative example 5 2 SEM image of section of @ PDA-RB.
FIG. 5 is EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 Graph of the nonlinear dielectric characteristic test result of @ PDA-OB.
FIG. 6 shows EP/BT @ TiO in examples 1 to 4 2 Graph of the nonlinear dielectric characteristic test result of @ PDA-OB.
FIG. 7 shows EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 Graph of results of testing nonlinear conductance characteristics of @ PDA-OB.
FIG. 8 shows EP/BT @ TiO in examples 1 to 4 2 Graph of nonlinear conductance test results of @ PDA-OB.
FIG. 9 shows EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 Breakdown field strength test result chart of @ PDA-OB.
FIG. 10 shows EP/BT @ TiO in examples 1 to 4 2 @ PDA-OB and EP/BT @ TiO in comparative examples 5 to 8 2 Breakdown field strength test result chart of @ PDA-RB.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
an epoxy composite material with nonlinear conductivity and dielectric property, the preparation method comprises the following steps:
1) Adding 3g of nano barium titanate particles (BT, with the particle size of 70-90 nm) into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 1h, adding 1.1mL of ammonia water with the mass fraction of 28%, magnetically stirring for 30min at 25 ℃, then dropwise adding 100mL of tetrabutyl titanate solution (prepared by mixing tetrabutyl titanate and absolute ethyl alcohol according to the volume ratio of 1:9), heating to 50 ℃, stirring at constant temperature for reaction for 24h, centrifuging at 9000rpm for 15min, washing the solid product obtained by centrifuging for multiple times by using deionized water and absolute ethyl alcohol alternately, drying in an oven at 80 ℃ for 24h, annealing at 550 ℃ in a muffle furnace under the air atmosphere for 3h to obtain BT @ TiO 2 A nanoparticle;
2) Dissolving 0.242g of Tris (hydroxymethyl) aminomethane (Tris) in 200mL of distilled water to prepare Tris buffer, and adding 2g of BT @ TiO 2 Dispersing nanoparticles with ultrasound for 1h, adding 0.6g dopamine hydrochloride, heating to 60 deg.C in dark, magnetically stirring at constant temperature for 24h, filtering, repeatedly washing the filtered solid product with deionized water, and freeze drying at-50 deg.C under 0.0001Pa for 30h to obtain BT @ TiO 2 @ PDA nanoparticles;
3) 10.5g of BT @ TiO 2 Adding @ PDA nano particles and 10.5g of boron nitride nano sheets (the sheet diameter is 100-600 nm) into 200mL of N, N-Dimethylformamide (DMF), ultrasonically dispersing for 1h, adding 100g of epoxy resin E51, heating to 100 ℃, stirring until the DMF is completely volatilized, adding 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole, injecting the obtained mixture into a stainless steel mold, placing the stainless steel mold into a constant-temperature oven at 105 ℃ for precuring for 60min, placing the stainless steel mold into a flat vulcanizing instrument, curing for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, heating to 135 ℃, and continuing to cure for 120min to obtain the epoxy composite material (marked as EP/@ TiO BT) with nonlinear conductivity and dielectric property 2 @PDA-OB， BT@TiO 2 The mass percentage of the @ PDA nano-particles is 5 percent, and the mass percentage of the boron nitride nano-sheets isThe amount was 5%).
Example 2:
an epoxy composite material with nonlinear conductivity and dielectric property, the preparation method comprises the following steps:
22.5g of BT @ TiO 2 The preparation process of the @ PDA nanoparticle is the same as that of example 1, 11.5g of boron nitride nanosheet (the sheet diameter is 100-600 nm) is added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, 100g of epoxy resin E51 is added, the temperature is raised to 100 ℃, stirring is carried out until the DMF is completely volatilized, 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mould, the stainless steel mould is placed in a constant-temperature oven at 105 ℃ for precuring for 60min, the mixture is placed in a flat-plate vulcameter, curing is carried out at 115 ℃ and 15MPa for 60min, the temperature is raised to 135 ℃, and then curing is carried out for 120min, so that the epoxy composite material with nonlinear electrical conductivity and dielectric property (marked as EP/BT @ TiO) is obtained 2 @PDA-OB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 10%, and the mass percentage of the boron nitride nano-sheets is 5%).
Example 3:
an epoxy composite material with nonlinear conductivity and dielectric property, the preparation method comprises the following steps:
50.5g of BT @ TiO 2 @ PDA nanoparticles (the preparation process is the same as that of example 1) and 12.5g of boron nitride nanosheets (the plate diameter is 100 nm-600 nm) are added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, then 100g of epoxy resin E51 is added, the temperature is increased to 100 ℃, stirring is carried out until the DMF is completely volatilized, then 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mould, then the stainless steel mould is placed in a constant temperature oven at 105 ℃ for precuring for 60min, then the stainless steel mould is placed in a flat plate vulcanizing instrument, curing is carried out for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, then the temperature is increased to 135 ℃, and then curing is continued for 120min, thus obtaining the epoxy composite material (marked as EP/BT/@ TiO) with nonlinear conductivity and dielectric property 2 @PDA-OB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 20%, and the mass percentage of the boron nitride nano-sheets is 5%).
Example 4:
an epoxy composite material with nonlinear conductivity and dielectric property, the preparation method comprises the following steps:
88g of BT @ TiO 2 @ PDA nanoparticles (the preparation process is the same as that of example 1) and 14.5g of boron nitride nanosheets (the plate diameter is 100 nm-600 nm) are added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, then 100g of epoxy resin E51 is added, the temperature is increased to 100 ℃, stirring is carried out until the DMF is completely volatilized, then 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mould, then the stainless steel mould is placed in a constant-temperature oven at 105 ℃ for precuring for 60min, then the stainless steel mould is placed in a flat-plate vulcanizing instrument, curing is carried out for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, then the temperature is increased to 135 ℃, and then curing is continued for 120min, so that the epoxy composite material (marked as EP/BT/@ TiO) with nonlinear conductivity and dielectric property is obtained 2 @PDA-OB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 30%, and the mass percentage of the boron nitride nano-sheets is 5%).
Comparative example 1:
an epoxy composite material, the preparation method comprises the following steps:
uniformly stirring 100g of epoxy resin E51, 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole, injecting the mixture into a stainless steel mold, placing the stainless steel mold into a constant-temperature oven, heating to 105 ℃, precuring for 60min, placing the stainless steel mold into a flat vulcanizing instrument, curing for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, heating to 135 ℃, and then continuously curing for 120min to obtain the epoxy composite material (marked as EP).
Comparative example 2:
an epoxy composite material, the preparation method comprises the following steps:
100g of epoxy resin E51, 81.7g of nano barium titanate particles (BT, with the particle size of 70 nm-90 nm), 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are uniformly stirred and injected into a stainless steel mold, then the stainless steel mold is placed in a constant-temperature oven, the temperature is raised to 105 ℃ for precuring for 60min, the stainless steel mold is placed in a flat-plate vulcanizing instrument, the epoxy composite material is firstly cured for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, and then the curing is continued for 120min after the temperature is raised to 135 ℃, so that the epoxy composite material (marked as EP/BT) is obtained.
Comparative example 3:
an epoxy composite material, the preparation method comprises the following steps:
100g of epoxy resin E51, 81.7g of BT @ TiO 2 Uniformly stirring and injecting the nano particles (the preparation process is the same as that of the example 1), 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole into a stainless steel mold, then placing the stainless steel mold into a constant-temperature oven, heating to 105 ℃, precuring for 60min, then placing the stainless steel mold into a flat-plate vulcanizing instrument, curing for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, heating to 135 ℃, and then continuing curing for 120min to obtain the epoxy composite material (marked as EP/BT @ TiO) 2 )。
Comparative example 4:
an epoxy composite material, the preparation method comprises the following steps:
100g of epoxy resin E51, 81.7g of BT @ TiO 2 @ PDA nano-particles (the preparation process is the same as that of example 1), 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are uniformly stirred, injected into a stainless steel mold, placed in a constant-temperature oven, pre-cured for 60min after being heated to 105 ℃, placed in a flat-plate vulcanizing machine, cured for 60min under the conditions that the temperature is 115 ℃ and the pressure is 15MPa, and then cured for 120min after being heated to 135 ℃ to obtain the epoxy composite material (marked as EP/BT @ TiO @ for 120 min) 2 @PDA)。
Comparative example 5:
an epoxy composite material, the preparation method comprises the following steps:
10.5g of BT @ TiO 2 Adding @ PDA nano particles (the preparation process is the same as that of example 1) and 10.5g of boron nitride nano sheets (the sheet diameter is 100-600 nm) into 200mL of N, N-Dimethylformamide (DMF), ultrasonically dispersing for 1h, adding 100g of epoxy resin E51, heating to 100 ℃, stirring until the DMF is completely volatilized, adding 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole, injecting the obtained mixture into a stainless steel mold, placing the stainless steel mold in a constant-temperature oven, heating to 105 ℃, pre-curing for 60min, heating to 115 ℃, curing for 60min, heating to 135 ℃, and continuously curing for 120min to obtain the epoxy composite material (note that the epoxy composite material is obtained) (the preparation process is the same as that of example 1)Is EP/BT @ TiO 2 @PDA-RB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 5%, and the mass percentage of the boron nitride nano-sheets is 5%).
Comparative example 6:
an epoxy composite material, the preparation method comprises the following steps:
22.5g of BT @ TiO 2 @ PDA nanoparticles (the preparation process is the same as that of example 1) and 11.5g of boron nitride nanosheets (the plate diameter is 100 nm-600 nm) are added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, then 100g of epoxy resin E51 is added, the temperature is increased to 100 ℃, stirring is carried out until the DMF is completely volatilized, then 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mold, then the stainless steel mold is placed in a constant-temperature oven, precuring is carried out for 60min after the temperature is increased to 105 ℃, curing is carried out for 60min after the temperature is increased to 115 ℃, curing is carried out for 120min after the temperature is increased to 135 ℃, and then the epoxy composite material (marked as EP/BT @ TiO) is obtained 2 @PDA-RB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 10%, and the mass percentage of the boron nitride nano-sheets is 5%).
Comparative example 7:
an epoxy composite material, the preparation method comprises the following steps:
50.5g of BT @ TiO 2 @ PDA nanoparticles (the preparation process is the same as that of example 1) and 12.5g of boron nitride nanosheets (the plate diameter is 100 nm-600 nm) are added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, then 100g of epoxy resin E51 is added, the temperature is increased to 100 ℃, stirring is carried out until the DMF is completely volatilized, then 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mold, then the stainless steel mold is placed in a constant-temperature oven, precuring is carried out for 60min after the temperature is increased to 105 ℃, curing is carried out for 60min after the temperature is increased to 115 ℃, curing is carried out for 120min after the temperature is increased to 135 ℃, and then the epoxy composite material (marked as EP/BT @ TiO) is obtained 2 @PDA-RB，BT@TiO 2 The mass percentage of the @ PDA nano-particles is 20%, and the mass percentage of the boron nitride nano-sheets is 5%).
Comparative example 8:
an epoxy composite material, the preparation method comprises the following steps:
88g of BT @ TiO 2 @ PDA nanoparticles (the preparation process is the same as that of example 1) and 14.5g of boron nitride nanosheets (the plate diameter is 100 nm-600 nm) are added into 200mL of N, N-Dimethylformamide (DMF), ultrasonic dispersion is carried out for 1h, then 100g of epoxy resin E51 is added, the temperature is increased to 100 ℃, stirring is carried out until the DMF is completely volatilized, then 90g of methylhexahydrophthalic anhydride and 0.7g of 2-ethyl-4-methylimidazole are added, the obtained mixture is injected into a stainless steel mold, then the stainless steel mold is placed in a constant-temperature oven, precuring is carried out for 60min after the temperature is increased to 105 ℃, curing is carried out for 60min after the temperature is increased to 115 ℃, curing is carried out for 120min after the temperature is increased to 135 ℃, and then the epoxy composite material (marked as EP/BT @ TiO) is obtained 2 @PDA-RB，BT@TiO 2 The mass percentage content of the @ PDA nano-particles is 30%, and the mass percentage content of the boron nitride nano-sheets is 5%).
And (3) performance testing:
1) Nano barium titanate particles (noted BT), BT @ TiO in example 1 2 Nanoparticles (noted BT @ TiO) 2 ) And BT @ TiO 2 @ PDA nanoparticles (noted as BT @ TiO) 2 @ PDA) is shown in fig. 1.
As can be seen from fig. 1: BT and BT @ TiO 2 3453cm in the FTIR spectrum of -1 The peak is related to the vibration of the hydroxyl groups on the surface of the particles, the presence of which contributes to the interaction with TiO 2 The shell and PDA shell form a covalent bond and are located at 570cm -1 And 1400cm -1 The peak corresponds to the Ti-O stretching vibration peak, and the surface of BT is coated with TiO 2 No new absorption peak appears after the shell, but the Ti-O absorption peak is obviously enhanced, which shows that TiO 2 The shell layer is successfully modified; BT @ TiO 2 FTIR spectra of @ PDA with BT and BT @ TiO 2 Compared with the FTIR spectrum of 1264cm -1 (aryl oxygen expansion) 1485cm -1 (-NH 3 + ) And 1632cm -1 Three new absorption peaks (N-H bending vibration) appeared, and in addition, at 3000cm -1 ～3700cm -1 The peak of the region became broader and higher, indicating an increase in hydroxyl groups and-NH after coating with PDA 2 The existence of radicals, i.e. successful coating of PDA shells on BT @ TiO 2 A surface.
2) BT @ TiO of example 1 2 @ PDA nanoparticles (Note)Is BT @ TiO 2 @ PDA) are shown in FIG. 2 (a is a transmission electron micrograph, b is a high-resolution transmission electron micrograph, and c to f are mapping photographs for elements Ba, ti, O, and N, respectively).
As can be seen from fig. 2: BT @ TiO 2 The @ PDA has two shells on the BT core; BT, tiO 2 And PDA from BT @ TiO 2 The HRTEM image of @ PDA is clearly distinguished; HRTEM image of BT core shows obvious lattice stripe, the interplanar spacing is 0.4nm, corresponding to (100) crystal face; tiO 2 2 Decoration of the shell showed (210) facets with an interplanar spacing of 0.205nm, confirming that there is TiO on the BT nanoparticles 2 A coating layer; the growth of the PDA shell can be found through the outer layer with an amorphous structure; BT and TiO 2 The elements of Ba, ti and O are present in BT @ TiO 2 @ PDA nanoparticle center region, where the unique N element of the PDA shell is also present in TiO 2 The successful modification of the PDA shell is shown on the surface of the shell, and the successful synthesis of BT @ TiO with a core-double shell structure is known in conclusion 2 @ PDA nanoparticles.
3) BT @ TiO in example 1 2 @ PDA nanoparticles (noted as BT @ TiO) 2 @ PDA) is shown in FIG. 3 (a is C1s spectrum, b is N1s spectrum, and C is O1s spectrum).
As can be seen from fig. 3: the C1s spectrum can be divided into 4 sub-peaks of 284.3eV (C-C/C-H), 285.7eV (C-N), 286.4eV (C-O) and 288.2eV (C = O), respectively, the presence of the binding energy of C-N and C = O indicates that PDA is in BT @ TiO @ 2 Self-polymerization occurs on the surface; the 399.2eV peak (C-N-H) in the N1s spectrum further illustrates the presence of PDA layers; C-O bonds can also be found in the O1s spectrum, and the appearance of Ti-O bonds at 529.6eV can be attributed to BT nuclei and TiO 2 And (4) a shell.
4) EP/BT @ TiO of example 1 2 @ PDA-OB and EP/BT @ TiO of comparative example 5 2 Scanning Electron Microscope (SEM) view of a cross section of @ PDA-RB is shown in FIG. 4 (a is EP/BT @ TiO 2 @ PDA-RB, b is EP/BT @ TiO 2 @ PDA-OB).
As can be seen from fig. 4: clearly dispersed BT @ TiO is observed in a 2 @ PDA nanoparticles and Boron Nitride Nanosheets (BNNSs), while b indicates that the edges were along during hot pressingThe vertical force, most BNNSs in the epoxy composite material after the hot pressing treatment show excellent parallel orientation, and in addition, the pre-curing treatment can improve the viscosity of the epoxy resin, thereby enhancing the extrusion force of the epoxy matrix to the BNNSs.
5) EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 The results of the non-linear dielectric characteristic test of @ PDA-OB are shown in FIG. 5, and EP/BT @ TiO in examples 1 to 4 2 The results of the non-linear dielectric characteristic test of @ PDA-OB are shown in FIG. 6.
As can be seen from fig. 5: the dielectric constant of pure epoxy resin (EP) is irrelevant to the electric field intensity, EP/BT shows obvious dielectric constant relevant to an electric field above 1.24kV/mm, and the dielectric constant of EP is improved from 3.1kV/mm to 4.1kV/mm due to the high dielectric constant of BT; due to strong interfacial polarization (BT-TiO) 2 Interface and TiO 2 PDA interface), tiO coated on BT core 2 Shell and PDA shell, obtained EP/BT @ TiO 2 And EP/BT @ TiO 2 The dielectric constant of @ PDA is respectively increased to 4.3kV/mm and 4.5kV/mm; BT @ TiO 2 The @ PDA nano-particles can be regarded as an independent capacitor, and space charge accumulation can be effectively relieved by adjusting interface polarization caused by huge difference between BT and an epoxy resin matrix; EP/BT @ TiO 2 @ PDA-OB still maintains the nonlinear dielectric characteristics, but its dielectric constant is significantly reduced, and thus it is known that introduction of BNNSs having high insulating properties and a low dielectric constant into the original epoxy system results in a reduction in dielectric constant.
As can be seen from fig. 6: EP/BT @ TiO 2 Dielectric constant of @ PDA-OB with BT @ TiO 2 @ PDA nanoparticle dosage was increased, the dielectric constant increased slowly with the increase of electric field at low load (5 wt% and 10 wt%) and the field-dependent nonlinear dielectric characteristic was weak, the dielectric constant increased rapidly with the increase of electric field at high load (20 wt% and 30 wt%) and exhibited strong field-dependent nonlinear dielectric characteristic, and further, the switching field at 30wt% load was decreased to 1.24kV/mm as compared to 20wt% load (1.68 kV/mm).
6) EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 The results of the non-linear conductance test of @ PDA-OB are shown in FIG. 7, and EP/BT @ TiO in examples 1 to 4 2 The results of the non-linear conductance test of @ PDA-OB are shown in FIG. 8, and EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in examples 2 to 4 2 Threshold field strength E of @ PDA-OB c And the nonlinear coefficient α are shown in table 1.
TABLE 1 threshold field intensity E c And a nonlinear coefficient alpha
As can be seen from fig. 7 and table 1: the electrical conductivity of EP and EP/BT both exhibit linear lg sigma-lg E characteristics, with BT nanoparticles being TiO coated 2 After coating of the inorganic semiconductor shell, EP/BT @ TiO 2 The material shows obvious nonlinear conductance characteristics, wherein the threshold field strength is 1.54kV/mm, and the nonlinear coefficient is 3.08; in addition, after the inorganic semiconductor shell is coated by the PDA organic semiconductor shell, EP/BT @ TiO 2 The nonlinear coefficient of @ PDA decreases to 2.30; as can be inferred from the above results, tiO 2 The current carriers provided by the housing may be shielded by the PDA housing; with the introduction of oriented BNNSs, EP/BT @ TiO due to the high insulating property of BNNSs 2 The conductivity and nonlinear coefficient of @ PDA-OB are further reduced, and at the same time, the threshold field intensity is increased to 2.29kV/mm, which indicates that BNNSs can influence the carrier transmission process and needs to realize carrier multiplication in a higher electric field.
As can be seen from fig. 8: BT @ TiO 2 EP/BT @ TiO with @ PDA nanoparticle content of 5wt% 2 @ PDA-OB exhibits a linearly dependent conductivity characteristic when BT @ TiO 2 The content of @ PDA nano particles reaches 10wt% or more, EP/BT @ TiO 2 The @ PDA-OB shows obvious field-dependent nonlinear conductance characteristics, and the result shows that BT @ TiO in nonlinear conductance composite material exists 2 Determined by the content of @ PDA nanoparticlesPercolation threshold, with BT @ TiO 2 Increase of nanoparticle content of @ PDA, BT @ TiO 2 The nanoparticle content of @ PDA will reach the percolation threshold, EP/BT @ TiO 2 @ PDA-OB exhibits field-dependent nonlinear conductance characteristics; BT @ TiO 2 EP/BT @ TiO 10wt%, 20wt% and 30wt% in @ PDA nanoparticle content 2 The non-linear coefficients of @ PDA-OB are 1.71, 1.75 and 1.99 respectively, the threshold field strengths are 2.75kV/mm, 2.39kV/mm and 2.29kV/mm respectively, and the results show that BT @ TiO 2 The higher the loading of the @ PDA nanoparticles, the higher the nonlinear coefficient, and the lower the threshold field strength.
7) EP in comparative example 1, EP/BT in comparative example 2, EP/BT @ TiO in comparative example 3 2 EP/BT @ TiO in comparative example 4 2 @ PDA and EP/BT @ TiO in example 4 2 FIG. 9 shows breakdown field strength characteristics of @ PDA-OB, and EP/BT @ TiO in examples 1 to 4 2 @ PDA-OB and EP/BT @ TiO in comparative examples 5 to 8 2 The breakdown field strength characteristic test results of @ PDA-RB are shown in FIG. 10.
As can be seen from fig. 9: EP has a breakdown field strength of 29.4kV/mm, with BT and BT @ TiO 2 The breakdown field strength is significantly reduced to 20.8kV/mm and 20.0kV/mm, indicating that the addition of a large amount of BT nanoparticles can introduce a large amount of interface defects in the epoxy resin matrix, despite the TiO 2 The shell can relieve the electric field distortion caused by the huge dielectric constant difference between BT and an epoxy resin matrix, but the inherent high conductivity of the shell can cause the mismatching of the conductivity between a filler and a polymer matrix, thereby accelerating the charge injection of an electrode and reducing the breakdown field strength, however, because the PDA shell enhances the adhesion of an interface and the epoxy resin matrix and improves the interface compatibility, the PDA modification is EP/BT @ TiO 2 The breakdown field strength of @ PDA is increased to 29.7kV/mm, which is higher than that of EP, and in addition, directionally arranged BNNSs can effectively reduce the conductivity and inhibit the development of electroosmotic flow path, so that the introduction of directionally arranged BNNSs adds EP/BT @ TiO 2 The breakdown field strength of @ PDA-OB continues to increase to 32.5kV/mm.
As can be seen from fig. 10: EP/BT @ TiO 2 @ PDA-RB and EP/BT @ TiO 2 Breakdown field intensity of @ PDA-OB composite material along with BT @ TiO 2 @ PDA nanoparticle contentIncrease first increasing and then decreasing, EP/BT @ TiO 2 @ PDA-OB in BT @ TiO 2 The breakdown field strength is as high as 45.7kV/mm when the content of the @ PDA nano-particles is 10wt%, and the EP is improved by 55%, compared with EP/BT @ TiO 2 The improvement of @ PDA-RB by 26% is noteworthy, at BT @ TiO 2 @ PDA nano-particles in the range of 5wt% -30 wt%, EP/BT @ TiO 2 The breakdown strength of @ PDA-OB is obviously higher than that of EP/BT @ TiO 2 And @ PDA-RB, which indicates that the breakdown field strength of the epoxy composite material can be obviously improved by the directional arrangement of the boron nitride nanosheets.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An epoxy composite material with non-linear electric conductance and dielectric property is characterized by comprising an epoxy resin matrix and filled BT @ TiO 2 @ PDA nanoparticles and filled boron nitride nanosheets; the BT @ TiO 2 The @ PDA nano-particle sequentially comprises a nano barium titanate core, a nano titanium dioxide coating layer and a polydopamine coating layer from inside to outside; the boron nitride nanosheets are transversely and directionally arranged in the epoxy resin matrix.
2. The epoxy composite having nonlinear electrical conductance and dielectric properties of claim 1, wherein: BT @ TiO in the epoxy composite material with nonlinear conductivity and dielectric property 2 The mass percentage content of the @ PDA nano-particles is 5-30%; the mass percentage of the boron nitride nanosheets in the epoxy composite material with nonlinear conductivity and dielectric property is 4-6%.
3. The epoxy composite having nonlinear electrical conductance and dielectric properties according to claim 1 or 2, wherein: the BT @ TiO 2 The particle size of the @ PDA nano-particles is 80 nm-100 nm.
4. The epoxy composite having nonlinear electrical conductance and dielectric properties according to claim 1 or 2, wherein: the sheet diameter of the boron nitride nanosheet is 100 nm-600 nm.
5. The epoxy composite having nonlinear electrical conductance and dielectric properties according to claim 1 or 2, wherein: the BT @ TiO 2 @ PDA nanoparticles were made by the following method:
1) Dispersing nano barium titanate particles in an organic solvent, adding ammonia water, adding tetrabutyl titanate solution for reaction,
then separating out solid product and annealing to obtain BT @ TiO 2 A nanoparticle;
2) Mixing BT @ TiO 2 Dispersing the nano particles in Tris buffer solution, adding dopamine hydrochloride, and reacting to obtain BT @ TiO 2 @ PDA nanoparticles.
6. The epoxy composite having nonlinear electrical conductance and dielectric properties of claim 5, wherein: the particle size of the nano barium titanate particles in the step 1) is 70-90 nm.
7. The epoxy composite having nonlinear electrical conductance and dielectric properties of claim 5, wherein: the reaction of the step 1) is carried out at the temperature of 40-60 ℃, and the reaction time is 20-30 h; the annealing treatment of the step 1) is carried out at 500-600 ℃, the annealing atmosphere is air atmosphere, and the annealing time is 2-4 h; the reaction in the step 2) is carried out at 50-70 ℃, and the reaction time is 20-30 h.
8. A method for preparing an epoxy composite material having nonlinear electrical conductivity and dielectric properties according to any one of claims 1 to 7, comprising the steps of: reacting BT @ TiO 2 Dispersing the @ PDA nano-particles and the boron nitride nano-sheets in an organic solvent, adding epoxy resin, heating and stirringStirring until the organic solvent is completely volatilized, adding a curing agent and an accelerant, injecting the obtained mixture into a mold, and then performing pre-curing and hot-pressing curing to obtain the epoxy composite material with nonlinear conductivity and dielectric property.
9. The method of claim 8, wherein: the mass ratio of the epoxy resin, the curing agent and the accelerator is 100.
10. Use of an epoxy composite material having nonlinear electrical conductivity and dielectric properties according to any one of claims 1 to 7 in high voltage electrical equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144268.3A CN115536982B (en) | 2022-09-20 | 2022-09-20 | Epoxy composite material with nonlinear conductivity and dielectric property, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144268.3A CN115536982B (en) | 2022-09-20 | 2022-09-20 | Epoxy composite material with nonlinear conductivity and dielectric property, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536982A true CN115536982A (en) | 2022-12-30 |
| CN115536982B CN115536982B (en) | 2023-07-18 |
Family
ID=84727459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211144268.3A Active CN115536982B (en) | 2022-09-20 | 2022-09-20 | Epoxy composite material with nonlinear conductivity and dielectric property, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536982B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831685A (en) * | 2021-09-16 | 2021-12-24 | 中国科学院工程热物理研究所 | Orientation-arranged boron nitride high-thermal-conductivity composite material and preparation method thereof |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090156715A1 (en) * | 2007-12-14 | 2009-06-18 | Thomas Eugene Dueber | Epoxy compositions comprising at least one elastomer and methods relating thereto |
| CN101712784A (en) * | 2009-10-29 | 2010-05-26 | 西安交通大学 | Nuclear shell structured packing/polymer-based composite material and preparation method thereof |
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| US20130337269A1 (en) * | 2011-03-07 | 2013-12-19 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, and prepreg as well as laminate using the same |
| US20150270067A1 (en) * | 2012-11-13 | 2015-09-24 | Kanto Denka Kogyo Co., Ltd. | Coated barium titanate particulate and production method for same |
| US20160016796A1 (en) * | 2009-08-14 | 2016-01-21 | Mark C. Hersam | Sorting Two-Dimensional Nanomaterials by Thickness |
| CN105315587A (en) * | 2015-11-27 | 2016-02-10 | 北京科技大学 | Polymer-based dielectric energy storage composite film material with core-shell structure and preparation method |
| US20160372263A1 (en) * | 2015-06-19 | 2016-12-22 | University Of Connecticut | Dielectric Materials Using 2D Nanosheet Network Interlayer |
| CN106566010A (en) * | 2016-10-25 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Silver-containing putamen graphene based dielectric elastic composite material and preparation method thereof |
| CN106832877A (en) * | 2016-12-26 | 2017-06-13 | 北京大学 | A kind of preparation method of vertical orientated boron nitride/high polymer insulating heat-conduction material |
| CN109467883A (en) * | 2018-11-06 | 2019-03-15 | 哈尔滨理工大学 | A kind of epoxy/inorganic nano combined High-heat-conductiviinsulation insulation material and preparation method thereof based on electric field induction sequence |
| JP2019089705A (en) * | 2019-01-28 | 2019-06-13 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Manufacturing method for dielectric ceramic particle and dielectric ceramic |
| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110092933A (en) * | 2019-05-28 | 2019-08-06 | 中国人民解放军陆军工程大学 | Field causes Invertible nonlinearity conducing composite material preparation method, obtained material and application |
| CN110938288A (en) * | 2019-12-09 | 2020-03-31 | 哈尔滨理工大学 | SiC @ SiO2Core-shell structured nano filler/epoxy resin-based composite material and preparation method thereof |
| CN112094482A (en) * | 2020-09-22 | 2020-12-18 | 浙江大学 | High-dielectric low-loss resin-based nanocomposite material for X waveband and method thereof |
| CN112175240A (en) * | 2020-10-14 | 2021-01-05 | 四川大学 | High-barrier high-breakdown water-resistant polymer composite film and preparation method and application thereof |
| CN112185703A (en) * | 2020-09-30 | 2021-01-05 | 同济大学 | High-breakdown and high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material and preparation method and application thereof |
| CN113121980A (en) * | 2021-04-20 | 2021-07-16 | 西南科技大学 | Composite material with high dielectric constant and energy storage density and preparation and application thereof |
-
2022
- 2022-09-20 CN CN202211144268.3A patent/CN115536982B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090156715A1 (en) * | 2007-12-14 | 2009-06-18 | Thomas Eugene Dueber | Epoxy compositions comprising at least one elastomer and methods relating thereto |
| US20160016796A1 (en) * | 2009-08-14 | 2016-01-21 | Mark C. Hersam | Sorting Two-Dimensional Nanomaterials by Thickness |
| CN101712784A (en) * | 2009-10-29 | 2010-05-26 | 西安交通大学 | Nuclear shell structured packing/polymer-based composite material and preparation method thereof |
| US20130337269A1 (en) * | 2011-03-07 | 2013-12-19 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, and prepreg as well as laminate using the same |
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| US20150270067A1 (en) * | 2012-11-13 | 2015-09-24 | Kanto Denka Kogyo Co., Ltd. | Coated barium titanate particulate and production method for same |
| US20160372263A1 (en) * | 2015-06-19 | 2016-12-22 | University Of Connecticut | Dielectric Materials Using 2D Nanosheet Network Interlayer |
| CN105315587A (en) * | 2015-11-27 | 2016-02-10 | 北京科技大学 | Polymer-based dielectric energy storage composite film material with core-shell structure and preparation method |
| CN106566010A (en) * | 2016-10-25 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Silver-containing putamen graphene based dielectric elastic composite material and preparation method thereof |
| CN106832877A (en) * | 2016-12-26 | 2017-06-13 | 北京大学 | A kind of preparation method of vertical orientated boron nitride/high polymer insulating heat-conduction material |
| CN109467883A (en) * | 2018-11-06 | 2019-03-15 | 哈尔滨理工大学 | A kind of epoxy/inorganic nano combined High-heat-conductiviinsulation insulation material and preparation method thereof based on electric field induction sequence |
| JP2019089705A (en) * | 2019-01-28 | 2019-06-13 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Manufacturing method for dielectric ceramic particle and dielectric ceramic |
| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110092933A (en) * | 2019-05-28 | 2019-08-06 | 中国人民解放军陆军工程大学 | Field causes Invertible nonlinearity conducing composite material preparation method, obtained material and application |
| CN110938288A (en) * | 2019-12-09 | 2020-03-31 | 哈尔滨理工大学 | SiC @ SiO2Core-shell structured nano filler/epoxy resin-based composite material and preparation method thereof |
| CN112094482A (en) * | 2020-09-22 | 2020-12-18 | 浙江大学 | High-dielectric low-loss resin-based nanocomposite material for X waveband and method thereof |
| CN112185703A (en) * | 2020-09-30 | 2021-01-05 | 同济大学 | High-breakdown and high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material and preparation method and application thereof |
| CN112175240A (en) * | 2020-10-14 | 2021-01-05 | 四川大学 | High-barrier high-breakdown water-resistant polymer composite film and preparation method and application thereof |
| CN113121980A (en) * | 2021-04-20 | 2021-07-16 | 西南科技大学 | Composite material with high dielectric constant and energy storage density and preparation and application thereof |
Non-Patent Citations (7)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831685A (en) * | 2021-09-16 | 2021-12-24 | 中国科学院工程热物理研究所 | Orientation-arranged boron nitride high-thermal-conductivity composite material and preparation method thereof |
| CN113831685B (en) * | 2021-09-16 | 2023-09-26 | 中国科学院工程热物理研究所 | Oriented boron nitride high-heat-conductivity composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536982B (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Thermal conductivity improvement of epoxy composite filled with expanded graphite | |
| Zhang et al. | Suppression of space charge in crosslinked polyethylene filled with poly (stearyl methacrylate)-grafted SiO2 nanoparticles | |
| CN113004474B (en) | Multi-walled carbon nanotube/barium titanate/polydicyclopentadiene composite material based on front-end ring-opening metathesis polymerization and preparation method thereof | |
| Feng et al. | Enhanced energy storage characteristics in PVDF-based nanodielectrics with core-shell structured and optimized shape fillers | |
| KR100791831B1 (en) | Manufacturing method of poly(epoxy-imide)-nano silica hybrid material via cs sol-gel process and the material | |
| CN115536982B (en) | Epoxy composite material with nonlinear conductivity and dielectric property, and preparation method and application thereof | |
| Chi et al. | SiC/SiO 2 filler reinforced EP composite with excellent nonlinear conductivity and high breakdown strength | |
| Wan et al. | Significantly enhanced dielectric and energy storage properties of plate-like BN@ BaTiO3 composite nanofibers filled polyimide films | |
| Dai et al. | Improved dielectric properties and energy density of PVDF composites using PVP engineered BaTiO 3 nanoparticles | |
| Li et al. | Dielectrical properties of graphite nanosheets/PVDF composites regulated by coupling agent | |
| Huang et al. | Preparation and characterizations of tantalum pentoxide (Ta2O5) nanoparticles and UV‐curable Ta2O5‐acrylic nanocomposites | |
| Su et al. | Polyvinyl butyral composites containing halloysite nanotubes/reduced graphene oxide with high dielectric constant and low loss | |
| Liu et al. | Optimizing electric field distribution via tuning cross-linked point size for improving the dielectric properties of polymer nanocomposites | |
| EP2402958B1 (en) | Electric isolation system for an electrical high voltage rotation machine | |
| Lai et al. | Effects and mechanism of graft modification on the dielectric performance of polymer–matrix composites | |
| Cai et al. | Enhanced Electromechanical Properties of Three‐Phased Polydimethylsiloxane Nanocomposites via Surface Encapsulation of Barium Titanate and Multiwalled Carbon Nanotube with Polydopamine | |
| CN113336978A (en) | Preparation method of epoxy micro-nano co-doped composite material | |
| Zheng et al. | High-k 3D-barium titanate foam/phenolphthalein poly (ether sulfone)/cyanate ester composites with frequency-stable dielectric properties and extremely low dielectric loss under reduced concentration of ceramics | |
| Xu et al. | Core-double-shell structured BT@ TiO2@ PDA and oriented BNNSs doped epoxy nanocomposites with field-dependent nonlinear electrical properties and enhancing breakdown strength | |
| Zeng et al. | Structural, dielectric and mechanical behaviors of (La, Nb) Co-doped TiO2/Silicone rubber composites | |
| Unnikrishnan et al. | Glass fiber reinforced bismaleimide/epoxy BaTiO3 nano composites for high voltage applications | |
| Zhang et al. | Dual crosslinked PMMA/BaTiO 3 polymer nanocomposite dielectrics for flexible film capacitors | |
| CN108485133B (en) | high-energy-storage-density composite material and preparation method thereof | |
| Xu et al. | Globally enhanced thermal, mechanical and electrical properties of current-field grading composites with self-assembly semiconducting grains on 3D cellulose aerogel scaffolds | |
| DE112019006442T5 (en) | CONDUCTIVE HEAT-CURING HIGH TEMPERATURE RESIN COMPOSITIONS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |